CN112573503B - Preparation method of nitrogen-doped porous carbon material, prepared porous carbon material and application thereof - Google Patents

Preparation method of nitrogen-doped porous carbon material, prepared porous carbon material and application thereof Download PDF

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CN112573503B
CN112573503B CN202011465510.8A CN202011465510A CN112573503B CN 112573503 B CN112573503 B CN 112573503B CN 202011465510 A CN202011465510 A CN 202011465510A CN 112573503 B CN112573503 B CN 112573503B
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郑方才
徐世凯
王俊中
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Anhui University
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Abstract

The invention discloses a preparation method of a nitrogen-doped porous carbon material, which relates to the technical field of nano material preparation, and comprises the following steps: (1) preparing a yellow precursor; (2) heating and carbonizing the yellow precursor at 600-700 ℃ for 2h at the speed of 10 ℃/min in a nitrogen atmosphere to obtain a black sample; (4) ultrasonically dispersing a black sample in deionized water, and then adding mixed acid for reflux etching; (5) and washing and drying the sample subjected to the reflux etching to obtain the nitrogen-doped porous carbon material. The invention also provides the material prepared by the method and application thereof. The invention has the beneficial effects that: the preparation method is safe and easy to implement, has short synthesis period, and can be used for mass preparation and is expected to be popularized and applied industrially.

Description

Preparation method of nitrogen-doped porous carbon material, prepared porous carbon material and application thereof
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of a nitrogen-doped porous carbon material, a prepared porous carbon material and application thereof.
Background
Lithium ion batteries are a type of portable electronic device energy storage system with high energy and power density. However, the potential for future applications is greatly hindered by geographical limitations and the increasing cost of lithium resources. In view of the uneven distribution of lithium resources and the scarcity of lithium resources in the earth's crust (20ppm), it is desirable to develop a rechargeable metal-ion battery based on low-cost and abundant elements on earth, such as sodium (23000ppm) potassium (17000 ppm). In addition, sodium and potassium have similar physicochemical properties and electrochemical reaction mechanisms as lithium, making SIBs and KIBs promising alternatives to LIBs. Therefore, it is crucial to explore reversible anode materials with suitable structures for high performance potassium ion batteries.
So far, a great deal of work is done on the design of potassium ion anode materials such as sulfide, selenide, phosphide, carbonaceous materials and the like at home and abroad. Among them, carbonaceous materials are attractive anodes for KIBs because of their advantages of environmental protection, low cost, abundant content, etc. To date, one of the effective strategies to improve potassium storage performance of carbonaceous materials is to adjust more active sites that adsorb potassium, however, few studies have focused on the ultra-potassium storage capacity formed by nanopores with a large number of N atom modifications on the inner surface.
The patent application with publication number CN110002424A discloses a nitrogen and oxygen co-doped porous carbon material, a preparation method and an application thereof, wherein a precursor is prepared from cobalt nitrate and 2-methylimidazole at normal temperature, the precursor is calcined in nitrogen to obtain a black material, the black material is treated by a hydrothermal oxidation method, and finally the obtained material is treated by nitric acid reflux to obtain a diatomic doped carbon material, namely the nitrogen and oxygen co-doped porous carbon material. But the prepared nitrogen and oxygen co-doped porous carbon material has poor stability.
Disclosure of Invention
The invention aims to solve the technical problem that the stability of a nitrogen and oxygen co-doped porous carbon material in the prior art is poor, and provides a preparation method of the nitrogen-doped porous carbon material.
The invention solves the technical problems through the following technical means:
a preparation method of a nitrogen-doped porous carbon material comprises the following steps:
(1) dissolving nickel chloride in methanol at room temperature to form a solution A, dissolving polyvinylpyrrolidone and 2-methylimidazole in methanol to form a solution B, mixing the solution A and the solution B under stirring, and standing for 24 hours; wherein the concentration of nickel chloride is 13.3-16.3mg/mL, the concentration of polyvinylpyrrolidone is 16.7-30mg/mL, and the concentration of 2-methylimidazole is 21.9-32.8 mg/mL;
(2) centrifuging the mixed solution in the step (1), and washing and drying a centrifuged product to obtain a yellow precursor;
(3) heating and carbonizing the yellow precursor in the step (2) at 600-700 ℃ for 2h at a speed of 10 ℃/min in a nitrogen atmosphere to obtain a black sample;
(4) ultrasonically dispersing a black sample in deionized water, and then adding mixed acid for reflux etching;
(5) and washing and drying the sample subjected to the reflux etching to obtain the nitrogen-doped porous carbon material.
Has the advantages that: the invention adopts nickel chloride and 2-methylimidazole to prepare precursor at normal temperature, polyvinylpyrrolidone is taken as surfactant in the preparation process, the dosage of methanol is adjusted, the formed precursor is nanospheres formed by sheet assembly,the carbon material formed by etching is a hollow carbon material with a hollow loose porous structure, a large number of nitrogen atoms are doped on the surface of the nano-pores, and the number of nitrogen atoms is K+Provides a large number of active sites, shortens electrons and K+The diffusion distance of the lithium ion battery has very high specific capacity and good cycling stability when used as a negative electrode material, and 167mAh/g can be kept after the lithium ion battery is cycled for 10000 times particularly in the charging and discharging process of large current 5A/g.
During the process of calcining the precursor, a large amount of carbon dioxide and water molecules overflow, so that the finally obtained nitrogen-doped porous carbon material has a loose and porous composite structure. The process for preparing the nitrogen-doped porous carbon material is simple, efficient, safe, easy to implement and short in synthesis period, and is expected to be popularized and industrially produced.
The precursor in the invention can not be obtained without adding polyvinylpyrrolidone in the preparation process, and the morphology of the precursor is changed into a spherical object composed of nano sheets after adding the precursor. If the amount of the methanol is too small, the nickel chloride and the 2-methylimidazole substances cannot be dissolved, and if the amount of the methanol is too large, waste is caused.
Preferably, the centrifuged product is washed with methanol and then dried at 60 ℃ for 6 h.
Preferably, the mixed acid in the step (4) is hydrochloric acid and nitric acid, and the volume ratio of the hydrochloric acid to the nitric acid is 1: 1.5.
Preferably, the reflow etching temperature is 80 ℃, and the reflow etching time is 6 h.
Preferably, the step (5) is performed by washing with deionized water and ethanol respectively.
Preferably, the drying temperature in the step (5) is 60 ℃ and the drying time is 6 h.
The invention also provides the nitrogen-doped porous carbon material prepared by the method, and the nitrogen-doped porous carbon material has a hollow porous structure.
Has the advantages that: the loose and porous structure is beneficial to the potassium ions and the electrolyte to enter and exit the active material; the hollow porous structure and the larger specific surface area structure can increase the contact area of the electrode material and the electrolyte and shorten the diffusion distance of lithium ions and the electrolyte; the doping of the high nitrogen atoms may improve the conductivity of the entire carbon material. When the lithium iron phosphate is used as a negative electrode material, the lithium iron phosphate has high specific capacity and good cycling stability, and can keep 167mAh/g after being cycled for 10000 times especially in the charge-discharge process of large current 5A/g.
Preferably, the specific surface area of the nitrogen-doped porous carbon material is 313-501m2/g。
The invention also provides an application of the nitrogen-doped porous carbon material prepared by the method as a potassium ion battery negative electrode material.
Has the advantages that: when the material is used as a negative electrode material, the material has high specific capacity and good cycling stability, and can maintain 167mAh/g after being cycled for 10000 times particularly in the charge and discharge process with large current of 5A/g.
Preferably, the preparation method of the potassium ion battery negative electrode material comprises the following steps: and mixing the nitrogen-doped porous carbon material, acetylene black and polyvinylidene fluoride into a slurry-like substance, coating the slurry-like substance on copper foil, and drying to obtain the electrode slice.
The invention also provides an application of the nitrogen-doped porous carbon material prepared by the preparation method in the preparation of a lithium ion battery.
Has the advantages that: according to the invention, the lithium ion battery is obtained by using the nitrogen-doped porous carbon material, and the discharge capacity of the battery can still be kept at 279mAh/g after the battery is tested under the condition that the current density is 1A/g and the battery is cycled for 2000 times. In the charging and discharging process of 5A/g, 167mAh/g can be maintained after circulation is carried out for 10000 times.
The invention has the advantages that: the invention adopts nickel chloride and 2-methylimidazole to prepare a precursor at normal temperature, polyvinylpyrrolidone is taken as a surfactant in the preparation process, the dosage of methanol is adjusted, the formed precursor is a nano sphere formed by sheets, the carbon material formed by etching is a hollow carbon material and has a hollow loose porous structure, the surface of the nano pore is doped with a large amount of nitrogen atoms at the same time, and the carbon material is K+Provides a large number of active sites, shortens electrons and K+The diffusion distance of (a).
During the process of calcining the precursor, a large amount of carbon dioxide and water molecules overflow, so that the finally obtained nitrogen-doped porous carbon material has a loose and porous composite structure. The process for preparing the nitrogen-doped porous carbon material is simple, efficient, safe, easy to implement and short in synthesis period, and is expected to be popularized and industrially produced.
When the material is used as a negative electrode material, the material has high specific capacity and good cycling stability, and can maintain 167mAh/g after being cycled for 10000 times particularly in the charge and discharge process with large current of 5A/g.
Compared with the prior art, the normal-temperature synthesis step is simpler, the yield is high, the material is more suitable for potassium electricity cathode materials, the potassium electricity cathode materials have higher requirements on the materials, the small current specific capacity reaches 409mAh, the number of circulating turns is 200 turns, the large current 5A/g circulating turns is 10000 turns and still remains stable, the multiplying power is good, and 244mAh g can be achieved under the current density of 5A/g-1。
Drawings
FIG. 1 is a scanning electron microscope image of a nitrogen-doped porous carbon material at a temperature of 600 ℃ in example 1 of the present invention; wherein the scale bar of a is 1 μm and the scale bar of b is 200 nm.
FIG. 2 is a TEM image of a nitrogen-doped porous carbon material with a temperature point of 600 ℃ in example 1 of the present invention; wherein the scale bar of c is 100nm and the scale bar of d is 200 nm.
FIG. 3 is a high-resolution TEM image of a nitrogen-doped porous carbon material with a temperature point of 600 ℃ in example 1 of the present invention; wherein e is 20nm on a scale and f is 100nm on a scale.
FIG. 4 is a transmission electron microscope image of a nitrogen-doped porous carbon material with a temperature point of 700 ℃ in example 1 of the present invention; wherein the scale bar for a is 0.2 μm and the scale bar for b is 200 nm.
FIG. 5 is an X-ray diffraction pattern of a nitrogen-doped porous carbon material at a temperature point of 600 ℃ and 700 ℃ in example 1 of the present invention; wherein the temperature point of a is 600 ℃ and the temperature point of b is 700 ℃.
FIG. 6 is a Raman diagram of a nitrogen-doped porous carbon material at a temperature point of 600 ℃ and 700 ℃ in example 1 of the present invention; wherein the temperature point of a is 600 ℃ and the temperature point of b is 700 ℃.
FIG. 7 is an X-ray photoelectron spectrum of a nitrogen-doped porous carbon material at a temperature of 600 ℃ and 700 ℃ in example 1 of the present invention;
fig. 8 is an adsorption-desorption graph of a nitrogen-doped porous carbon material at a temperature point of 600 ℃ and a temperature point of 700 ℃ in example 1 of the present invention; wherein the temperature point of a is 600 ℃ and the temperature point of b is 700 ℃.
FIG. 9 is a graph showing discharge capacity and cycle number of a half-cell obtained by nitrogen-doping a porous carbon material at 600 and 700 ℃ in example 2 of the present invention; wherein the discharge current density is 100mA/g, the temperature point of a is 600 ℃, and the temperature point of b is 700 ℃.
FIG. 10 is a graph showing discharge capacity and cycle number of half cells obtained in example 2 of the present invention, in which the discharge current density is 1A/g;
FIG. 11 is a graph showing the capacity and the cycle at different discharge current densities of a half-cell obtained by using a nitrogen-doped porous carbon material at 600 ℃ and 700 ℃ in example 2; wherein the temperature point of a is 600 ℃ and the temperature point of b is 700 ℃.
FIG. 12 is a graph showing discharge capacity and cycle number of a half-cell obtained by nitrogen-doping a porous carbon material at 600 and 700 ℃ in example 2 of the present invention; wherein the discharge current density is 5A/g.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method of the nitrogen-doped porous carbon material comprises the following steps:
(1) dissolving 237mg of nickel chloride in 15mL of methanol at room temperature to form a solution A; polyvinylpyrrolidone 300mg and 328mg 2-methylimidazole were dissolved in 15mL of methanol to form solution B, and solution A and solution B were slowly dropped together with stirring. The mixture was stirred for 5 minutes and then allowed to stand at room temperature for 24 hours.
(2) The prepared sample was centrifuged, washed three times with methanol and then dried in an oven at 60 ℃ for 6h to give a yellow precursor.
(3) Then, the prepared precursor is carbonized for 2 hours at a heating rate of 10 ℃/min under the conditions of 600 ℃ and 700 ℃ in a nitrogen atmosphere to obtain two black samples.
(4) The black sample was ultrasonically dispersed in 30mL of deionized water, and then 10mL of hydrochloric acid and 15mL of nitric acid were added to the solution. The resulting solution was transferred to a 100ml round bottom flask and kept under reflux at 80 ℃ for 48 hours.
(5) And centrifugally separating the product, washing the product with deionized water and ethanol for three times respectively, and then drying the product in an oven at the temperature of 60 ℃ for 6 hours to obtain the nitrogen-doped porous carbon material at the temperature point of 600 ℃ and the nitrogen-doped porous carbon material at the temperature point of 700 ℃ respectively.
FIGS. 1 to 3 are Scanning Electron Microscope (SEM) photographs, Transmission Electron Microscope (TEM) photographs and high resolution transmission photographs (HRTEM) of the final product obtained in this example at a temperature point of 600 ℃ respectively. As can be seen from the SEM images of fig. 1(a, b), the final product produced consisted of a large number of spherical particles, roughly between 50 and 100nm in size. As can be seen from the TEM images of fig. 2(c, d), the prepared polyhedrons contain a large number of holes. These voids are caused by the evolution of large amounts of small molecule gases (e.g., nitrogen dioxide, carbon dioxide, water molecules) during carbonization. As can be seen from fig. 3(e, f) HRTEM, polyhedrons were prepared containing a large number of distinct lattice stripes of carbon material. FIG. 4 shows a transmission electron microscope with a temperature point of 700 ℃ and also spherical particles similar to the temperature point of 600 ℃.
FIG. 5 shows the X-ray diffraction pattern of the final product obtained in this example
Figure BDA0002834019820000081
Figure (a). As can be seen from fig. 5a and 5b, the diffraction peak around 25 ° in the figure is a diffraction peak of a typical (002) crystal plane of the carbon material. In addition, the peak at 25 ° is relatively strong and broad, and crystallinity attributable to nitrogen and the doped porous carbon material is relatively good. The degree of graphitization of the resulting composite material can be determined by raman spectroscopy.
FIG. 6 is a Raman spectrum of the final product obtained in this example. From the Raman spectrum, it can be seen that the peak intensities are at 1350 and 1580cm-1The two peaks at (A) can be respectively assigned to the D band and the G band typical of carbon materials.
FIG. 7 is an X-ray photoelectron spectrum of the final product obtained in this example. As can be seen from an X-ray photoelectron spectrum, the final product contains three atoms of carbon, nitrogen and oxygen, and further indicates that the nitrogen-doped carbon material is prepared. In addition, the results of X-ray photoelectron spectroscopy revealed that the atomic proportions of nitrogen and oxygen at 600 ℃ were 8.49 and 14.31%, respectively, in the final product, and 6.20 and 13.22%, respectively, at 700 ℃.
Fig. 8 is a nitrogen adsorption-desorption graph of the final product obtained in this example. As can be seen from the nitrogen adsorption-desorption graph, the nitrogen-doped carbon material with the temperature point of 600 ℃ has a porous structure and the specific surface area of 500.58m2G, and a specific surface area of 313.97m at 700 DEG C2/g。
Example 2
The method for preparing the potassium ion battery cathode material by adopting the nitrogen-doped porous carbon material in the embodiment 1 specifically comprises the following steps:
mixing a nitrogen-doped porous carbon material, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10 to prepare a slurry-like substance, then coating the slurry-like substance on a copper foil, drying the copper foil in an oven at 80 ℃, and cutting the copper foil into a circular electrode slice with the diameter of 14mm, namely the lithium ion battery cathode material.
Example 3
The potassium ion battery prepared by the potassium ion battery negative electrode material in the embodiment 2 specifically comprises the following steps:
the electrode sheet in example 2 was used as a positive electrode, a circular metal potassium sheet with a diameter of 14mm was used as a negative electrode, a mixed solution containing 3mol/L potassium bis-fluorosulfonylimide KFSI, which was prepared by mixing ethylene carbonate EC and diethyl carbonate DEC in a mass ratio of 1:1, was used as an electrolyte, and a circular polypropylene film with a diameter of 16mm was used as a separator, and a button cell was assembled in a glove box protected by argon atmosphere to serve as a test cell.
It was tested for Newware BTS-610 using a battery test system. As shown in FIG. 9(a), the discharge capacity was maintained at 409mAh/g after 200 cycles at a temperature point of 600 ℃ and a current density of 100 mA/g.
As shown in FIG. 10, the discharge capacity of the test cell was maintained at 279mAh/g after 2000 cycles at a current density of 1A/g.
The rate test of fig. 11(a) is also an important parameter for measuring the stability of a battery. The half-cells prepared in this example were tested at current densities of 0.1,0.2,0.4,0.6,0.8,1,2, and 5A g, respectively-1The specific capacities are 480,451,417,398,376,345,307 and 244mAh g respectively-1。
FIG. 9(b) the discharge capacity was maintained at 377mAh/g at a temperature point of 700 ℃. FIG. 11(b) shows the current densities of the test cells at 0.1,0.2,0.4,0.6,0.8,1,2, and 5A g-1The specific capacities are 375,293,247,221,204,188,162and 87mAh g respectively-1This result shows that the half cell in this example has better stability.
FIG. 12 shows that 167mAh/g can be maintained after 10000 cycles in the charge and discharge process of 5A/g.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. A preparation method of a nitrogen-doped porous carbon material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving nickel chloride in methanol at room temperature to form a solution A, dissolving polyvinylpyrrolidone and 2-methylimidazole in methanol to form a solution B, mixing the solution A and the solution B under stirring, and standing for 24 hours; wherein the concentration of nickel chloride is 13.3-16.3mg/mL, the concentration of polyvinylpyrrolidone is 16.7-30mg/mL, and the concentration of 2-methylimidazole is 21.9-32.8 mg/mL;
(2) centrifuging the mixed solution in the step (1), and washing and drying a centrifuged product to obtain a yellow precursor;
(3) heating and carbonizing the yellow precursor in the step (2) at 600-700 ℃ for 2h at a speed of 10 ℃/min in a nitrogen atmosphere to obtain a black sample;
(4) ultrasonically dispersing a black sample in deionized water, and then adding mixed acid for reflux etching;
(5) washing and drying the sample subjected to the reflux etching to obtain a nitrogen-doped porous carbon material;
the mixed acid in the step (4) is hydrochloric acid and nitric acid, and the volume ratio of the hydrochloric acid to the nitric acid is 1: 1.5;
the reflux etching temperature is 80 ℃, and the reflux etching time is 6 hours.
2. The method for producing a nitrogen-doped porous carbon material according to claim 1, characterized in that: the centrifuged product was washed with methanol and then dried at 60 ℃ for 6 h.
3. The method for producing a nitrogen-doped porous carbon material according to claim 1, characterized in that: and (5) washing with deionized water and ethanol respectively.
4. The method for producing a nitrogen-doped porous carbon material according to claim 1, characterized in that: the drying temperature in the step (5) is 60 ℃, and the drying time is 6 h.
5. A nitrogen-doped porous carbon material produced by the production method according to any one of claims 1 to 4, characterized in that: the nitrogen-doped porous carbon material has a hollow porous structure.
6. Use of the nitrogen-doped porous carbon material prepared by the preparation method according to any one of claims 1 to 4 as a negative electrode material of a potassium ion battery.
7. The use of the nitrogen-doped porous carbon material as a negative electrode material for a potassium ion battery according to claim 6, wherein: the preparation method of the potassium ion battery negative electrode material comprises the following steps: and mixing the nitrogen-doped porous carbon material, acetylene black and polyvinylidene fluoride into a slurry-like substance, coating the slurry-like substance on copper foil, and drying to obtain the electrode slice.
8. Use of the nitrogen-doped porous carbon material prepared by the preparation method of any one of claims 1 to 4 in the preparation of a lithium ion battery.
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